Ruthenium complexes 7-acetylide

The formation of complexes 109 has been shown to proceed via a vinylidene ruthenium intermediate (112), which has been indirectly isolated by protonation of an acetylide-ruthenium complex (112). Arene ruthenium vinylidene complexes 113 appear to be much more reactive than their isoelectronic (C5H5)(R3P)2Ru=C=CHR+ complexes (63,66). 

Dimeric association (71) can be obtained by an acid-base reaction between alkyl zirconocene and a terminal alkynyl ruthenium complex (equation 32). Surprisingly, the same reaction was observed with an iron acetylide opposed to Schwartz s reagent see Schwartz s Reagent) (equation 33). ... 

Figure 7. Protic-switching of cubic NLO response.s in ruthenium cr-acetylide/vinylidene complexes. The imaginary component of the second hyperpolarizability y i.s related to cr, [112]...

T-acetylide ruthenium complexes with the [Ru (ri -C5R5)L2] fragment (C5R5 = cyclopentadienyl, indenyl L2 = mono- or bisphosphines) as the electron donor group. These complexes display in the visible intense MLCT absorptions, which dominate the (3 responses, and, compared with... 

In this kind of bimetallic chromophores, another efficient electron-donor group is a ruthenium o-acetylide complex [13, 19] which can lead to large jSi.oeCHRS)... 

Two (cyclopentadienyl)bis(phosphine)ruthenium chloride complexes have been investigated the nonlinearities are low. These results have been used in conjunction with measured nonlinearities of acetylenes and acetylide complexes to demonstrate that values for the latter are not simply the sum of the molecular components (see earlier). An example of a metal... 

Interestingly, the in situ generated ruthenium acetylide complex C5Me5(PPh3)Ru-C=CPh catalyzed the cross-coupling reaction of terminal and internal alkynes to yield functionalized enynes [87] (Eq. 65). A coordinatively unsaturated enynyl complex is postulated as an intermediate in this mechanism. 

In contrast to the lithium acetylide reaction, addition of copper(I) phenylacetylide to (i75-C5H5)(PPh3)2RuCl (1) affords the monomeric ruthenium acetylide-copper chloride adduct (62) as the major product. An X-ray crystal structure of this complex reveals an tj1, -bridging acetylide between the ruthenium and copper centers, respectively (62). A small amount of the dimeric chloride bridged complex 61 was also isolated. The copper chloride can be removed from the monomeric complex by the... 

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